JPH11116814A - Polyoxyalkylene-modified polyorganosilsesquioxane resin and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyorganosilsesquioxane resin having excellent storage stability even in the form of an emulsion and exhibiting excellent coating property to various substrates without causing cissing trouble. SOLUTION: This resin contains amino group, polyoxyalkylene group and alkoxy group in one molecule and is expressed by the formula (R<1> is a univalent hydrocarbon residue which may be substituted with halogen atom; R<2> is a 1-4C alkyl; R<3> is a 1-4C alkyl or 1-4C alkoxy; X is (CH2 )3 or (CH2 )3 NH(CH2 )2 ; R<4> is a 2-4C alkylene; 5<=q<=30; Y is an alkyl ether, an alkyl phenyl ether, methacryloyl or acryloyl group; (m) is 1-50; (n) is 1-50; (p) is 15-500). The resin can be dispersed in water by the addition of water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyoxyalkylene-modified polyorganosilsesquioxane resin containing an amino group in the same molecule. More specifically, the present invention has excellent storage stability and emulsifying properties, and further has a short coating film. Formed stably under low temperature heating or room temperature conditions for hours, glass, tile,
Solvent-free and water-based media for use on cement-based structural materials, hull bottoms, rubber, leather, plastics, wood, and other surfaces, especially where organic solvents are undesirable due to their toxicity and fire hazard. The present invention relates to a polyoxyalkylene-modified polyorganosilsesquioxane resin having an amino group in the same molecule, which can be used and whose formed film has weather resistance, wound shielding property, water resistance, and stain resistance.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION AND PROBLEMS OF THE INVENTION Conventionally, silsesquioxane resins have been widely used as coating materials and the like. Regarding the method for producing a silsesquioxane emulsion, a method of adding an organosilane to a surfactant, a catalyst and water has been proposed (see Japanese Patent Publication No. 52-12219).
This requires a dropping facility for adding the organosilane, and it is necessary to gradually add the organosilane over a long period of time because of difficult control of the addition conditions. In this case, even in this method, many gel substances are generated during the dropping of the organosilane,
This is disadvantageous in that the product is filtered, taken out, and the yield of the product is low, resulting in poor economic efficiency. Japanese Patent Application Laid-Open No. 60-20959 discloses the production of a liquid low-molecular silicone emulsion containing an alkoxy functional group, which discloses an emulsifying method and an emulsifying composition. This is intended only for building hydrophobic materials, and promotes curing of residual alkoxy groups and silanol groups in combination with a catalyst.
Defect occurs in stability when used as a liquid. Furthermore, Japanese Patent Application Laid-Open No. 3-95228 discloses organofunctional polydiorganosiloxanes containing an amino group and a polyoxyethylene group, but the polymer in this publication is synthesized by an addition reaction, The inclusion of alkoxy is not essential. Therefore, the siloxanes of this publication are:
It is difficult to form a film stably at room temperature and at low temperature. As in the above-mentioned conventional techniques, the emulsification of a reactive substance in the existing technique is difficult to stably exist in water for a long period of time using a main material having a reactive group and a curing catalyst in combination. In use, two or more components must be mixed and used at the time of use, and improvements have been desired from the viewpoint of a decrease in working efficiency and poor stability over time of the mixture. Further, in the case of paints and coating compositions using an organic solvent as a solvent, there are problems of safety during handling and environmental hygiene, so that an emulsion-type treating agent using water as a dispersant has been desired.

[0003]

The object of the present invention is to solve the above-mentioned problems of the prior art, and to form a film having excellent water repellency, weather resistance and antistatic properties by applying it to various substrates and heating it at low temperature at room temperature or for a short time. Also, it can be used as a solvent-free coating solution using water as a dispersing agent, so there is no problem in terms of safety and environmental hygiene due to organic solvents. It is an object of the present invention to provide a polyorganosilsesquioxane resin showing good coating properties without cissing on a material.

[0004]

As a result of various studies to achieve the above object, the present invention has found a polyoxyalkylene-modified polyorganosilsesquioxane resin containing an amino group in the same molecule. It came to be. That is, the present invention is a polyoxyalkylene-modified polyorganosilsesquioxane resin having an amino group, a polyoxyalkylene group and an alkoxy group in one molecule represented by the following general formula,

[0005]

Embedded image

(Wherein, R ¹ is a monovalent hydrocarbon residue optionally substituted by a halogen atom, R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms. Alkyl group and / or
Or alkoxy group, X is, - (CH _{2) 3} - or - (CH _{2) 3} NH
(CH ₂ ) ₂ -group, R ⁴ is an alkylene group having 2 to 4 carbon atoms, q
Is a number of 5 ≦ q ≦ 30, Y is an alkyl ether, alkylphenyl ether, methacryloyl and / or acryloyl group, m is a number of 1 to 50, n is a number of 1 to 50, p
Indicates a number of 15 to 500. And (A) a compound represented by the general formula: R ¹ Si (OR ² ) ₃ (wherein R ¹ is a monovalent hydrocarbon residue optionally substituted with a halogen atom, and R ² is alkyl having 1 to 4 carbon atoms) 1 mole of the alkoxysilane represented by
Adding 0.5 to 0.95 mol obtained by performing the partial hydrolysis, the average molecular weight to an alkoxy group-containing polymethylsilsesquioxane 100 parts by weight of 700 to 10000 (B) the general formula NH ₂ XSi (OR ³ ) ₃ and / or NH ₂ XSiR ³ (O
R ³⁾ ₂ (wherein, X is - (CH _{2) 3} - or _{- (CH 2) 3 NH (} CH 2) 2 - group,
R ³ represents an alkyl group having 1 to 4 carbon atoms) and 0.01 to 10 parts by weight of an amino group-containing alkoxysilane represented by the formula (C): Y— (R ⁴ O) _q R ⁵ (where Y is An alkyl ether, an alkylphenyl ether, a methacryloyl and / or an acryloyl group, wherein R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, R ⁵ is a hydrogen atom and / or an alkyl group having 1 to 4 carbon atoms, q
Represents a number of 5 ≦ q ≦ 30), 0.05 to 100 parts by weight of a polyoxyalkylene having a hydroxyl group and / or an alkoxy group at a terminal, and heating at 50 to 90 ° C. to perform a condensation reaction. A method for producing the above polyoxyalkylene-modified polyorganosilsesquioxane resin. The resin of the present invention is a resin that can be used without a solvent, and can be used by dispersing it in water as required. Furthermore, the present inventor has conducted various studies on a method for obtaining the above resin stably and economically. As a result, the organotrialkoxysilane and / or a partial hydrolyzate thereof contains a specific amino group-containing silane and / or Using a partial hydrolyzate in combination with a hydroxyl group and / or an alkoxy group at the terminal of a polymer having a specific polyoxyalkylene group to obtain a silicone resin that can be used in a solvent-free and water-dispersible manner without generating or sedimenting a gelled product. I found that I can do it.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The component (A) used in the polyorganosilsesquioxane resin of the present invention has a general formula R ¹ Si (OR ² ) ₃ (where R ¹ is a monovalent carbon atom which may be substituted with a halogen atom). A hydrogen residue, R ² represents an alkyl group having 1 to 4 carbon atoms),
It is an alkoxy group-containing polymethylsilsesquioxane having an average molecular weight of 700 to 10,000 obtained by performing partial hydrolysis by adding 0.5 to 0.95 mol. R ^{1 in the} component (A) is a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different. Examples of such substituted or unsubstituted monovalent hydrocarbon groups include those having 1 to 1 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, decyl group and dodecyl group. 12 alkyl groups; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group and xylyl group; 1 such as aralkyl group such as β-phenylethyl group and β-phenylpropyl group. Examples thereof include a substituted hydrocarbon group having a valence, and among these, a methyl group is preferable because of availability of raw materials. (A) OR of component
Reference numeral ² denotes an alkoxy group having 1 to 4 carbon atoms. Among them, a methoxy group and an ethoxy group are preferable because of a low odor of by-products generated during the curing reaction and excellent curability and film properties. Such an alkoxy group-containing polymethylsilsesquioxane can be easily obtained by a known method. That is, methyl trialkoxysilane, alkoxysilanes such as phenyltrialkoxysilane and the alkyl group of the alkylalkoxysilane is an ethyl group,
Alkyl groups having 1 to 12 carbon atoms such as propyl group, butyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group; alkenyl groups such as vinyl group and allyl group; tolyl group, xylyl group An aryl group such as
One or a mixture of organosilicon compounds substituted with a monovalent hydrocarbon group such as an aralkyl group such as a phenylethyl group or a β-phenylpropyl group, or a mixture thereof is appropriately selected. It is obtained by adding 0.5 to 0.95 mol of water to 1 mol of alkoxysilane in the presence and performing partial hydrolysis. As a catalyst for synthesizing the above resin, organic acids such as acetic anhydride, glacial acetic acid, propionic acid, benzoic acid, formic acid, acetic acid and oxalic acid; titanates such as tetrabutyl titanate; methyltrichlorosilane and dimethyldichlorosilane Chlorosilanes; inorganic bases such as aqueous ammonia; and organic bases such as ethylenediamine and triethanolamine. The component (A) has an average molecular weight of 700 to 1000.
0 is preferable, and particularly preferably it is 1,000 to 5,000. If the average molecular weight is less than 700, it is difficult to form a stable film, and if it exceeds 10,000, it is difficult to modify, which is not preferable. It is also possible to include D unit and Q unit silane as necessary as a liquid resin containing an alkoxy group. As the silane of the D unit,
Examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. Examples of the silane of the Q unit include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane. As the component (A), the curable polyorganosiloxanes obtained as described above and having different properties may be used as a composite blend.

(B) used in the silicone resin of the present invention
The components are of the general formula NH ₂ XSi (OR ³ ) ₃ and / or NH ₂ XSiR ³ (O
R ³ ) A silane represented by ₂ and / or a partial hydrolyzate thereof, and is a component involved as a catalyst and an adhesion improver in the resin of the present invention. In component (B), X is
-(CH ₂ ) _3- or-(CH ₂ ) ₃ NH (CH ₂ ) ₂ -group, R ³ has 1 to 1 carbon atoms
4 represented by an alkyl group. The component (B) used in the present invention includes, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltripropoxysilane, and N, as examples of the general formula NH ₂ XSi (OR ³ ) _3. -(Β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-
γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltripropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-amino as examples of the general formula NH ₂ XSiR ³ (OR ³ ) ₂ Propylmethyldiethoxysilane, γ-aminopropylmethyldipropoxysilane, N- (β-aminoethyl) -γ
-Aminopropylmethyldimethoxysilane, N- (β-
Aminoethyl) -γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldipropoxysilane, and the like. Or N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane. The component (B) used in the present invention is a catalyst component for forming a film and a component for improving adhesion. This is essential for condensing the resin of the present invention and bringing it into close contact with the substrate. Component (B) is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of component (A). If the amount is less than 0.01 part by weight, the catalytic effect related to the film formation is deteriorated and the adhesion to the substrate is inferior, and if it exceeds 10 parts by weight, the liquid stability when dispersed in water is inferior. Is not preferred.

(C) used in the silicone resin of the present invention
The component has a general formula Y- (R ⁴ O) _q R ⁵ (wherein, Y represents an alkyl ether, an alkylphenyl ether, a methacryloyl and / or an acryloyl group, and R ⁴ represents an alkylene group having 2 to ⁴ carbon atoms; R ⁵ is a hydrogen atom and / or an alkyl group having 1 to 4 carbon atoms,
q represents a number satisfying 5 ≦ q ≦ 30), is a polyoxyalkylene having a hydroxyl group and / or an alkoxy group at a terminal, and is another important component that characterizes the present invention. This component is mainly a component for stably dispersing the resin of the present invention in water, but is also a component for imparting toughness and an antistatic effect to the film. In the component (C), q must be a number satisfying the following relationship. If 5 ≦ q ≦ 30 q is less than 5, the stability when the resin is dispersed in water is poor, which is not suitable for the purpose of the present invention. On the other hand, if it is larger than 30, it is difficult to be taken into the silicone resin by hydrolysis (condensation reaction), and when the film is formed, unreacted components bleed out of the film, which is not preferable. Examples of the compound having such a polyoxyalkylene group include polyoxyethylene lauryl ether, polyoxyethylene dodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether,
Ether types such as polyoxyethylene oleyl ether; alkylphenyl ether types such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether; polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate Ester type; further, monomethacrylate types such as methoxydiethylene glycol methacrylate and methoxypolyethylene glycol methacrylate; monoacrylates such as methoxypolyethylene glycol acrylate; and the like, but not limited thereto, and various known types. Or a combination of two or more thereof. Among these, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, or methoxy polyethylene glycol acrylate is preferable because of stability during emulsification and easy availability. (C)
The amount of the component used is 0.05 to 10 with respect to 100 parts by weight of the component (A).
0 parts by weight. If the amount used is less than 0.05 part by weight, the liquid stability when dispersed in water will cause a problem, and if it exceeds 100 parts by weight, it will be difficult to be taken into the film, and when the film is formed, this component as an oil component It is not preferable because it precipitates out of the coating and causes problems such as impairing the transparency.

The resin of the present invention is obtained by blending the components (A), (B) and (C) in the above-mentioned ratio and heating at 50 to 90 ° C. to carry out a condensation reaction. But 1.380-1.
520, a polyoxyalkylene-modified polyorganosilsesquioxane resin containing an amino group in the same molecule. The reactivity of the resin of the present invention can be confirmed by 1) the presence or absence of absorption of a hydroxyl group in 3500 Kaiser by infrared absorption spectrum (IR). The reaction was terminated when the hydroxyl group disappeared (IR before the reaction).
Chart (Fig. 1) and IR chart after reaction (Fig. 2)
reference). 2) Those having 15 or more polyoxyalkylene chains are in a suspended state before the reaction, but become transparent as the reaction proceeds. 3) Resin is added to city water, and reactivity is confirmed by its dispersion state. If unreacted, separation of oil occurs. 4) It can be confirmed by the change in molecular weight by gel permeation chromatography.

The resin of the present invention can be used by dispersing it in water. The proportion is preferably such that the amino group-containing alkoxysilane of the component (B) is 5% by weight or less based on water. Amino group-containing alkoxysilane is 5
Exceeding the weight% is not preferable because it causes gelation under the influence of the activity of the amino group.

[0012] The silicone resin of the present invention comprises the above (A)
It consists of a co-hydrolysis reaction of the components (B) and (C), in which various auxiliary components can be incorporated. As such auxiliary components, for example, pigments and ultraviolet absorbers for the purpose of altering or smelling the contents by visible light or ultraviolet light, coloring agents such as dyes, leveling agents,
Examples include inorganic powders and various flavors.

The silicone resin of the present invention can be used for protecting glass, plastics, outer wall materials, etc., for soil-repelling agents such as cement-based structural materials, and for repelling water; for releasing molded articles such as rubber and wood; It can be used as an antistatic agent as an internal additive or a surface treatment agent in acrylic paints, urethane paints, polyester paints, epoxy paints, vinyl chloride paints, acrylic melamine paints, and alkit melamine paints, and as a glossing agent. .

The silicone resin of the present invention can be used as an emulsifier for emulsifying another silicone resin. The silicone resin and the aqueous dispersion of the silicone resin of the present invention can be applied to a substrate by a method such as spray coating, brush coating, dipping, roll coating, and flow coating.

[0015]

The polyoxyalkylene-modified polyorganosilsesquioxane resin having an amino group in the molecule according to the present invention is applied to various base materials, and has excellent water repellency by heating at room temperature or for a short time at a low temperature. Forms a film having weather resistance and antistatic properties. In addition, since it can be used as a coating solution using no solvent or water as a dispersant, there is no problem in terms of safety and environmental hygiene caused by an organic solvent. Shows good coating properties without cissing. Further, it has an excellent effect as an emulsifier for emulsifying other silicone components, and has a very large practical value from the viewpoint of environmental problems and the like.

[0016]

The present invention will be described in more detail with reference to the following examples. Unless otherwise specified, all amounts in Examples, Synthesis Examples and Comparative Examples are parts by weight, and viscosities are values at 25 ° C. Synthesis Example 1 In a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a heating jacket, 136 g (1.0 mol) of methyltrimethoxysilane, 20.0 g of methanol and methyltrichlorosilane were added so that the hydrogen chloride content was 50 ppm. While charging and stirring, 17.1 g (0.95 mol) of water was gradually added dropwise using a dropping funnel. 4 at reflux temperature (about 68-72 ° C)
After holding for a time, hydrolysis and condensation reactions were performed. Then, after the volatile components were distilled off under the conditions of normal pressure and a liquid temperature of 100 ° C., the pressure was gradually reduced, and the volatile components were further distilled off under reduced pressure of 40 Torr and a liquid temperature of 150 ° C. Then, 63.0 g (A-1) of a polyorganosiloxane shown in Table 1 was obtained. However, the organic group content a, X group content b in the table
Is a value calculated based on the charged compounding amounts of the silane compound and water (the same applies to the following synthesis examples).

Synthesis Example 2 A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and heating jacket was charged with the silane compound and the hydrolysis catalyst in the amounts shown in Table 1 and gradually heated with stirring. When the liquid temperature reached 80 ° C., the amount of water shown in Table 1 was gradually added dropwise. The solution was maintained at a liquid temperature of 80 ° C. for 6 hours to carry out hydrolysis and condensation reactions. Then, after evaporating the volatile components under the conditions of normal pressure and a liquid temperature of 130 ° C., the pressure was gradually reduced, and the volatile components were further distilled off under reduced pressure of 30 Torr and a liquid temperature of 130 ° C. Return to the polyorganosiloxane (A-2, A-3, A-4 and A-5) shown in Table 1.
I got

[0018]

[Table 1]

Example 1 Polyorganosiloxane (A-1) 100 obtained in Synthesis Example 1
g, N- (β-aminoethyl) -aminopropylmethyldimethoxysilane 2 g, nonionic surfactant polyoxyethylene nonylphenyl ether (Nikkol NP18TX)
; Nikko Chemicals Co., Ltd.) was charged into a 500-ml flask equipped with a stirrer, thermometer and reflux condenser, and heated and stirred at 80 to 85 ° C for 4 hours. Thereafter, volatile components were distilled off under reduced pressure at a pressure of 30 Torr and a liquid temperature of 60 ° C., and the pressure was returned to normal pressure to obtain a silicone resin (S-1). The end point of the reaction was determined by a change in appearance (unreacted: cloudy, progress of the reaction: transparent solution), infrared absorption spectrum (IR), and gel permeation chromatography (GPC). The hydroxyl group of the surfactant disappears by IR and G
As shown in PC, it can be confirmed that the two peaks became one and the two peaks were condensed. When these conditions were satisfied, the reaction was completed.

Examples 2 to 5 Polyorganosiloxane synthesized in the above synthesis examples
Based on (A-2 to 5), a silane having an N- (β-aminoethyl) -aminopropyl group and a nonionic surfactant were charged in proportions shown in Table 2, and the same operation as in Synthesis Example 1 was performed. Then, silicone resins (S-2 to 5) were obtained.

[0021]

[Table 2]

Comparative Example 1 95.2 g (0.7 mol) of methyltrimethoxysilane and 19.8 g of phenyltrimethoxysilane were placed in a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and heating jacket.
g (0.1 mol), 51.6 g (0.4 mol) of dimethyldichlorosilane, and 120.0 g of toluene.
23.4 g (1.3 mol) was gradually added dropwise using a dropping funnel. After completion of the dropwise addition, the mixture was heated and refluxed at a liquid temperature of 110 ° C. for 1 hour.

The reaction solution is cooled to room temperature, transferred to a separating funnel and allowed to stand to separate an organic layer and an aqueous layer. The lower aqueous layer is removed, and a toluene solution of polyorganosiloxane is added. Obtained. A saturated saline solution was added to the toluene solution, and the mixture was stirred well, and then allowed to stand to separate an aqueous layer. After repeating this salting-out operation twice, water was added and the organic layer was washed twice with the same operation. The organic layer thus obtained was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a heating jacket and a Teen Turn Stark separation tube, and the pressure was reduced to 30 To.
The volatile components were distilled off under reduced pressure at rr and a liquid temperature of 80 ° C. to obtain a polyorganosiloxane (B-1). Example of synthesis using B-1
When the same operation as (A-1) was performed, (B-1: 100 g, Ni
kkol NP18TX; 70 g, N- (β-aminoethyl) -aminopropylmethyldimethoxysilane: 2 g) A large amount of gel was generated, and the desired silicone resin could not be obtained.

Comparative Example 2 Polyorganosiloxane (A-1) 100 obtained in Synthesis Example 1
g, 70 g of a nonionic surfactant, polyoxyethylene nonylphenyl ether (Nikkol NP18TX; product of Nikko Chemicals Co., Ltd.), and 2 g of tetrabutoxytitanate, with an inner volume of 500 g equipped with a stirrer, thermometer and reflux condenser.
Then, the mixture was charged into a ml flask, and heated and stirred at 80 to 85 ° C. for 4 hours. Thereafter, the volatile components were distilled off under reduced pressure at a reduced pressure of 30 Torr and a liquid temperature of 60 ° C., and the pressure was returned to normal pressure to obtain a silicone resin (E-1).

Comparative Example 3 Polyorganosiloxane (A-1) 100 obtained in Synthesis Example 1
g, N- (β-aminoethyl) -aminopropylmethyldimethoxysilane 2 g, nonionic surfactant polyoxyethylene nonylphenyl ether (Nikkol NP18TX)
; Nikko Chemicals Co., Ltd.) 150 g was charged into a 500-ml flask equipped with a stirrer, thermometer and reflux condenser, and heated and stirred at 80 to 85 ° C for 4 hours.
Thereafter, volatile components were distilled off under reduced pressure at a reduced pressure of 30 Torr and a liquid temperature of 60 ° C., and the pressure was returned to normal pressure to obtain a silicone resin (E-2).

Comparative Example 4 Polyorganosiloxane (A-2) 100 obtained in Synthesis Example 2
g, N- (β-aminoethyl) -aminopropylmethyldimethoxysilane, 20 g, nonionic surfactant, polyoxyethylene nonylphenyl ether (Nikkol NP18TX)
; Nikko Chemicals Co., Ltd.) was charged into a 500 ml flask equipped with a stirrer, thermometer and reflux condenser, and heated and stirred at 80 to 85 ° C for 4 hours. Thereafter, volatile components were distilled off under reduced pressure at a reduced pressure of 30 Torr and a liquid temperature of 60 ° C., and the pressure was returned to normal pressure to obtain a silicone resin (E-3).

[Preparation of Test Specimens] The compositions of the present invention and the compositions of Comparative Examples were prepared with the compositions shown in the table, and the shielding properties, weather resistance, water resistance, aesthetic appearance, oil floating, and stability were as follows. evaluated. The evaluation results are shown in the table. [Preparation of Test Piece] A glass plate and an aluminum plate having a size of 15 cm × 15 cm were lightly rubbed with sandpaper to make abrasion. The coating agent was wiped with an air gun and dried for one day to form a film, thereby preparing a test piece. [Shielding Property] The appearance of the test piece was visually observed and evaluated according to the following four grades. ：: The abrasion part is well shielded, and the transparency of the film is good. ○: A part of the abrasion part is exposed, but the transparency of the film is good. Δ: A part of the abrasion part is exposed, and the transparency of the film is good. Slightly poor x: Insufficient shielding effect, no transparency of film [Weather resistance] 500 using sunshine weatherometer
The appearance after exposure for a time was visually observed and evaluated according to the following four grades. ：: The abrasion part is well shielded, and the transparency of the film is good. ○: A part of the abrasion part is exposed, but the transparency of the film is good. Δ: A part of the abrasion part is exposed, and the transparency of the film is good. Slightly poor x: Insufficient shielding effect and no clearness of film [Aesthetics] After leaving the test piece to stand at 25 ° C and 60% relative humidity for 2 months, visually observe the appearance and observe the following. Was evaluated in four steps. ：: The transparency of the film is good and there is no adhesion of dust. ○: The transparency of the film is good, but some adhesion of dust is observed. △: The transparency of the film is slightly poor and some adhesion of dust is seen. X: Insufficient transparency of the film and adhesion of dust [Oil floating property] The test piece was immersed in cold water for 14 hours, and the presence or absence of oil floating was visually observed and evaluated according to the following three grades. ◎: No oil floating ○: Slight oil floating ×: Oil floating [Stability] 50% of coating agent and silicone resin
After standing at ℃ for 3 months, the appearance of the solution and the uniformity of the solution were visually observed and evaluated according to the following three grades. ◎: Good homogeneity of liquid ○: Slight generation of microgel is observed ×: Partial separation of liquid is observed Evaluation result

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

[0031]

[Table 6]

[0032]

[Table 7]

[0033]

[Table 8]

[0034]

[Table 9]

[0035]

[Table 10]

As is apparent from the above, the polyoxyalkylene-modified polyorganosilsesquioxane resin having an amino group in the molecule of the present invention is excellent in that it can be applied to various substrates to form a film. It has good shielding properties, weather resistance and the like. In addition, since no solvent is used, and furthermore, water can be used as a dispersant, there is no concern about safety due to an organic solvent, there is no problem in environmental hygiene, and further, it has excellent storage stability when it is made into an emulsion. . It has excellent storage stability even when it is made into an emulsion, and shows good coating properties without cissing on various substrates. Further, it has an excellent effect as an emulsifier for emulsifying other silicone components, and has a very large practical value from the viewpoint of environmental problems and the like.

[Brief description of the drawings]

FIG. 1 is a view showing an IR chart before a reaction of a resin of the present invention.

FIG. 2 is a view showing an IR chart after the reaction of the resin of the present invention.

Claims (5)

[Claims] 1. A polyoxyalkylene-modified polyorganosilsesquioxane resin having an amino group, a polyoxyalkylene group and an alkoxy group in one molecule represented by the following general formula. Embedded image (Wherein, R ¹ represents 1 which may be substituted with a halogen atom)
R ² is an alkyl group having 1 to 4 carbon atoms, R ³ is an alkyl group and / or alkoxy group having 1 to 4 carbon atoms, and X is-(CH ₂ ) _3- or- (CH ₂ ) ₃ NH (CH ₂ ) ₂ -group, R ⁴ is an alkylene group having 2 to 4 carbon atoms, q is a number of 5 ≦ q ≦ 30, Y is an alkyl ether, an alkylphenyl ether,
A methacryloyl and / or acryloyl group, m represents a number of 1 to 50, n represents a number of 1 to 50, and p represents a number of 15 to 500; ) 2. A polyoxyalkylene-modified polyorganosilsesquioxane resin according to claim 1, which is mixed with water.
Water-dispersed polyoxyalkylene-modified polyorganosilsesquioxane resin. 3. A paint comprising the polyoxyalkylene-modified polyorganosilsesquioxane resin according to claim 1 as a main component. 4. A water-dispersible paint comprising the water-dispersed polyoxyalkylene-modified polyorganosilsesquioxane resin according to claim 2 as a main component. 5. A compound of the general formula R ¹ Si (OR ² ) _{3 wherein} R ¹ is a monovalent hydrocarbon residue which may be substituted by a halogen atom, and R ² has 1 to 4 carbon atoms. Water) with respect to 1 mol of the alkoxysilane represented by
Adding 0.5 to 0.95 mol obtained by performing the partial hydrolysis, the average molecular weight to an alkoxy group-containing polymethylsilsesquioxane 100 parts by weight of 700 to 10000 (B) the general formula NH ₂ XSi (OR ³ ) ₃ and / or NH ₂ XSiR ³ (OR ³ ) ₂ (wherein X is a — (CH ₂ ) ₃ — or — (CH ₂ ) ₃ NH (CH ₂ ) ₂ — group and R ³ is 0.01 to 10 parts by weight of an amino group-containing alkoxysilane represented by 4 represents an alkyl group) and (C) the general formula Y- (in R ⁴ O) _q R ⁵ (wherein, Y is an alkyl ether, alkyl phenyl ether, A methacryloyl and / or acryloyl group; R ⁴ is an alkylene group having 2 to ⁴ carbon atoms; R ⁵ is a hydrogen atom and / or an alkyl group having 1 to 4 carbon atoms;
Represents a number of 5 ≦ q ≦ 30), 0.05 to 100 parts by weight of a polyoxyalkylene having a hydroxyl group and / or an alkoxy group at a terminal, and heating at 50 to 90 ° C. to perform a condensation reaction. The method for producing a polyoxyalkylene-modified polyorganosilsesquioxane resin according to claim 1, characterized in that: